KR950000036B1 - Enhanced livingness of polymerization using silylated oxyanions - Google Patents

Abstract

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Description

[Name of invention]

Process for preparing “active” polymers using silylated oxy anions

Detailed description of the invention

The present invention relates to a process for polymerizing polar αolefin monomers into "active" polymers and to "active" polymers prepared by such methods.

Techniques known as electrotransfer polymerization are described in U.S. Pat. Described in The former uses their preparations from "active" polymers and acrylic-type or maleimide monomers, with defined organosilicon, -tin or -germanium initiators and catalysts that are either sources of fluoride, cyanide or azide ions or are suitable Lewis acids. To claim. The latter is similar but uses a source of bifluoride ions as promoter.

Both disclose various suitable solvents for catalysts including acetonitrile, which are used in amounts comprising 19 moles per catalyst and more. Acetonitrile is also used in higher amounts as a general solvent for polymerization.

By "active" polymer is meant a polymer of the invention which contains at least one active terminal group and is capable of polymerizing in the presence of monomer (s) and a promoter. "Activity" and "livingness" are written in quotation marks to distinguish them from their biological meanings.

In an attempt to further benefit using electromechanical polymerization, it would be desirable to find a way to extend or increase the duration of the "activity" of the polymerization. This involves somewhat reducing the ratio of termination to further polymerization. This can lead to high molecular weight, low polydispersity and good control and predictability of molecular weight.

Related applications include serial numbers 660,588, 660,589. 673.926 and 676,099. In addition, US Pat. No. 4,588,795 discloses and claims the use of certain types of oxyanion catalysts in electrotransfer polymerization, and US Pat. No. 4,622,372 discloses and claims the enhancement of the activity of these oxyanions with acetonitrile or silylated acetonitrile. However, it can sometimes bind some catalyst and thus slow down the polymerization compared to the rate when all catalysts are available.

The present invention relates to quaternary organics having at least one polar acrylic-type alpha olefin monomer under polymerization conditions (i) having at least one active substituent or activated radical attached and optionally having one or more substituents which are inert under polymerization conditions. Silicon, organotin or organogermanic polymerization initiator, and (ii) contact with a catalyst wherein the acid is a salt consisting of an oxyanion or an oxyanion with an appropriate cation with a pKa of about 5 to about 24 (DMSO), (iii ) No activating substituents or activating diradicals are attached thereto, at least one equivalent of R ₃ Si-group (R optionally contains one or more ether oxygen atoms in its aliphatic component, One or more functional substituents which are not reactive under polymerization conditions may optionally contain ether oxygen atoms. A polymer selected from the group consisting of 0-silylated esters or ether modifications of oxyanion compounds having a pKa (DMSO) of about 5-24, but not a polymerization initiator, containing hydrocarbyl of up to 20 carbon atoms) Provided is a method of preparing an "active" polymer, which is also characterized in contact with an activity enhancer.

Preferably, the catalyst is tetra (n-butyl) ammonium 3-chloro benzoate (TBA-CB) or tetra (n-butyl) ammonium bi-3-bichloro benzoate (TBA-biCB) and the enhancer is 3-chloro benzo Trimethyl silyl ester of eights.

Preferred concentrations of enhancer range from at least about 0.1 or about 0.1-1000 moles, preferably 0.1-200, sometimes optionally 5-25 or 0.2-2,5 per mole of catalyst.

Preferred conjugate acids of the oxyanion catalyst have a pKa (DMSO) of about 6-21, more preferably 8-18. Preferably the pKa of the activity enhancer is less than or equal to the pKa of the catalyst.

Polymers prepared by the process of the present invention are characterized by polymerization in the presence or presence of a component containing such a metal at the "active" end and an activating substituent or diradical or its tautomer at the "inactive" end of the polymer. It is "active" in that it is erased.

Useful monomers here have the formula CH ₂ = C (Y) X wherein X is -CN, -CH = CHC (O) X 'or -C (O) X', and Y is -H, -CH ₃ , -CN or -CO ₂ R, provided that Y is -H or -CH ₃ when X is -CH = CHC (O) X '; X 'is -OSi (R ¹ ) ₃ , -R, -OR or -NR'R''; Each R ¹ is independently H or an hydrocarbyl radical that is an aliphatic, cycloaliphatic, aromatic or mixed aliphatic-aromatic radical containing up to 20 carbon atoms, provided that at least one R ¹ group is not H; R is a hydrocarbyl radical which is an aliphatic, cycloaliphatic, aromatic or mixed aliphatic-aromatic radical containing up to 20 carbon atoms or a polymer radical containing at least 20 carbon atoms, either of which one or more ethers in the aliphatic moiety One or more reactive substituents, optionally containing oxygen atoms, optionally containing one or more functional substituents which are non-reactive under polymerization conditions, and having the formula -Z '(O) CC (Y ¹ ) = CH ₂ Optionally wherein Y ¹ is H or CH ₃ and Z 'is 0 or NR'; Each R 'and R''are independently selected from C _1-4 alkyl.

The initiators used in the polymerization of the present invention are the silicon-containing initiators of specifications serial numbers 660,588, 660,589, 673,926 and 676,099 pending in U.S. Patents 4,414,372, 4,524,196, 4,417,034, and 4,508,880. Preferred initiators for use herein have a formula selected from (R ¹ ) ₃ MZ, (R ¹ ) ₂ M (Z ¹ ) ₂ and O [M (R ¹ ) ₂ X ¹ ] ₂ , wherein R ¹ is As defined above; Z is

이고 ; m은 2, 3 또는 4이고 ; n은 3, 4 또는 5이며 ; M은 Si, Sn 또는 Ge이며, 단 Z가Is an activating substituent selected from the group consisting of -OP [OSi (R ¹ ) ₃ ] ₂ and mixtures thereof, wherein R, R ¹ , R ', R ", X' and Z 'are as defined above. Z 'is an active substituent -OC =

ego ; m is 2, 3 or 4; n is 3, 4 or 5; M is Si, Sn or Ge, provided that Z is

When M is Sn or Ge; Each R ² and R ³ is independently selected from H and hydrocarbyl as defined above for R; (a) at least one of any of R, R ² and R ³ in the opener optionally contains one or more initiating substituents having the formula -Z ² -M (R ¹ ) ₃ , wherein M and R ¹ are As defined above; Z ² is

인 경우에 M은 Sn 또는 Ge이며, (b) Z가

또는 -OC=C(R²)(R³)-이고/거나 Z²가

이면, 함께 취해진 R²와 R³는

이고 ; (c) Z가

또는

이고/거나 Z²가

이면, X'와 함께 취해진 R²또는 R³는

이다.Activating diradicals selected from the group consisting of mixtures thereof, wherein R ² , R ³ , X ', Z', m and n are as defined above, provided that Z ² is

Where M is Sn or Ge, (b) Z is

Or -OC = C (R ² ) (R ³ )-and / or Z ² is

If R ² and R ³ taken together

ego ; (c) Z is

or

And / or Z ²

If R ² or R ³ taken with X '

to be.

By conjugate acid is meant an acid formed by protonation of catalytic oxyanions. For example, the conjugate acid of the acetate anion is acetic acid and the biacetate anion is acetic acid dimer.

The conjugate acid is pKa (DMSO) is the negative logarithm of the acidity constant of the conjugate acid measured in dimethylsulfoxide (DMSO) at 25 ° C. Methods for determining the pKa values of various acidic compounds, including oxyacids, are described abundantly in the literature, for example in F.G.Bodwell, J. Org.Ghem., 45, 3305 (1980); 46, 4327 (1981); 47, 3224 (1982) and 49, 1424 (1984).

[Description of Enhancement of Activity as Silylated Oxyanion]

이 1.0에 접근)와 구축이 잘 조절된 블록 공중합체를 제조할 수 있으며, 그러나 단, 자기-종결반응이 조절될 수 있을 경우이다. 그러한 자기-종결반응은 중합체 쇄의 조기종결을 초래하며, 이는 결과 중합체에 여러가지 영향을 야기한다.Group transfer polymerization (GTP) is an "active" polymerization in that monomer units continue to be added to the ends of the growing polymer chain and there is no chain transfer and ideally no termination. In this way we use a monodisperse polymer (

Approach to 1.0) and well-controlled block copolymers can be made, provided that the self-termination can be controlled. Such self-termination leads to premature termination of the polymer chain, which results in a variety of effects on the resulting polymer.

For example, the molecular weight distribution of the linear polymer will be wide (the degree of dispersion will be at least 1). Linear polymers made with multiple monomer feeds exhibit a multi-modal molecular weight distribution, where the molecular weight of each peak shown in the distribution corresponds to the amount of active polymer remaining at the beginning of each successive monomer feed. In the star block copolymer (monofunctional monomer which is blocked with a small amount of difunctional monomer to provide crosslinking of the active chain of the monofunctional polymer), the polymer chain terminated before the addition of the bifunctional monomer in the phase forming step. There will be an amount of low molecular weight polymer corresponding to the amount. Similarly, in the linear block copolymer some of the homopolymer of the first monomer will be present at the end of the polymerization.

Acetonitrile and silylated acetonitrile appear to enhance the activity of some GTP polymerizations when used in controlled amounts. Silylethers or esters of oxyanion GTP catalysts can also control the activity of GTP polymerization and are much more effective in this function than acetonitrile or silylacetonitrile, especially at high polymerization temperatures.

For some purposes, it is desirable but not necessary to combine the silylated oxyanion materials with a suitable oxyanion catalyst. For example, trimethylsilyl 3-chlorobenzoate is preferably used with tetra (n-butyl) ammonium 3-chlorobenzoate catalyst.

One example of a silylation modification of an oxyanion compound that is an initiator and is therefore excluded in the (iii) part of the claims is a silylated (2-trialkylsilyl) acetate ester.

및

)은 겔투과 크로마토그래피(GPC)로 측정되었다. 중합체의 다분산성은 (

)으로 정의된다. GPC로 결정된 피크분자량(M_p)은 또한 여러 경우로 보고된다. 중합의 정도(D_p)는 또한 사용된 여러 단량체에 대해 보고된다. 달리 지정되지 않는 한, 얻어지는 모든 "활성" 중합체 생성물은 준자량을 결정하기 전에 수증기나 메탄올에 노출시켜 냉각하였다. 모든 온도는 섭씨도이다. 모든 부, 비율 및 백분율은 달리 지적하지 않는 한 중량기준이다.In the following recipes and comparisons, the median and number average molecular weights of the polymer products (each

And

) Was measured by gel permeation chromatography (GPC). The polydispersity of the polymer is (

Is defined as Peak molecular weights (M _p ) determined by GPC are also reported in several cases. The degree of polymerization (D _p ) is also reported for the various monomers used. Unless otherwise specified, all “active” polymer products obtained were cooled by exposure to water vapor or methanol before determining the quasi-quantity. All temperatures are in degrees Celsius. All parts, ratios and percentages are by weight unless otherwise indicated.

[Preparation 1]

Preparation of Trimethylsilyl-3-chlorobenzoate

38.05g 3-chlorobenzoic acid and 56.53g hexamethyldisilazine in 250ml round bottom three-necked flasks with condenser, thermocouple, N ₂ inlet, and polytetrafluoroethylene (PTFE) coated magnetic-stering bars Charged. The mixture was heated to reflux and refluxed for 8 hours until ammonia evaporation stopped. Excess hexamethyldisilazine was squeezed from the reaction mixture at 50 mmHg through a sidearm condenser until the temperature of the flask contents reached 125 ° C.

[Comparative 1]

Preparation of MMA // EGDM (D _p -100 // D _p -4) star polymers (D _p = degree of polymerization)

The monomers and solvents used were prepared as follows. Tetrahydrofuran (THF) was prepared (purified) by distillation with sodium / benzophenone immediately before use. Methyl methacrylate (MMA) and ethylene glycol dimethacrylate (EGDM) were prepared through a neutral anhydrous alumina column and MMA was subsequently distilled with calcium hydride at 100 mm Hg and stored at 0 ° C. for up to 1 week. 1-trimethylsiloxy-1-methoxy-2-methylpropene was prepared by 2-rotation-distillation (50 mmHg).

A 250 ml round bottom three-necked flask equipped with a condenser, thermocouple, N ₂ and vacuum inlet and mechanical stirrer was dried with a heating gun under vacuum (5 mmHg) and allowed to cool under N ₂ purge. The apparatus was placed in a 50 ° C. water bath, charged with 117.5 g of THF and equilibrated to 50 ° C. After equilibration, 0.325 ml of a THFso 0.353 mol solution of 1.015 g of 1-trimethylsiloxy-1-methoxy-2-methylpropene and tetra (n-butyl) ammonium 3-chlorobenzoate was further charged into the flask. Two minutes after charging tetra (n-butyl) ammonium 3-chlorobenzoate into the reaction flask, a 30 minute supply of 60.08 g of MMA was started. The reaction temperature was maintained at 50 ° C. ± 0.5 ° C. during the feed. After completion of the VMMA feed, the contents of the flask were held at 50 ° C. ± 0.5 ° C. for 30 minutes. At this time, 4.45 g of EGDM was fed into the reaction flask over 10 minutes. The contents of the reaction flask were maintained at 50 ° C. ± 0.7 ° C. during EGDM feed. One hour after the end of the EGDM feed, methanol (5 ml) and toluene (0.432 g) were charged to the flask.

After addition of methanol and toluene no EGDM or MMA remained detectable by high pressure liquid chromatography (HPLC). The molecular weight distribution obtained by gel permeation chromatography (GPC) was bimodal, the low molecular weight fraction (11,000 M _p ) constituted 40 weight percent polymer and the high molecular weight fraction (180,000 M _p ) the remaining 60 weight percent Was constructed.

Example 1

Preparation of MMA // EGDM (D _p- 100 // D _p- 4) Star Polymer with TMS-CB

The monomers and solvents used were prepared as follows. THF was prepared by distillation with sodium / benzophenone immediately before use. MMA and EGDM were prepared by passing through a column of neutral anhydrous alumina and MMA was subsequently distilled with calcium hydride (100 mmHg) and stored at 90 ° C. for up to one week. 1-trimethylsiloxy-1-methoxy-2-methylpropene was prepared by 2-rotation-distillation (50 mmHg).

A 250 ml round bottom three-necked flask with condenser, thermocouple, N ₂ and vacuum inlet and mechanical stirrer was dried with a heating gun under vacuum (5 mmHg) and cooled under N ₂ purge. The apparatus was placed in a 50 ° C. water bath, charged with 116.01 g of THF, equilibrated to 50 ° C., followed by 0.325 ml of a 0.353-ol solution of tetra (n-butyl) ammonium 3-chlorobenzoate in THF, 1- 1,023 g of triethylsiloxy-1-1-ethoxy-2-methylpropene and 1.140 ml of a 0.0961 molar solution of triethylsilyl-3-chlorobenzoate (TMS-CB) in THF were added. Two minutes after the addition of TMS-CB, a 30 minute feed of 58.46 g of MMA was initiated. The reaction contents were held at 50 ° C. Q0.7 ° C. for 30 minutes during the feed and after the termination of the MMA feed. 30 minutes after the end of the MMA feed, a 10 minute feed of EDGM 4.61 g was started. The reaction contents were maintained at 50 ° C. Q0.5 ° C. during this feed. One hour after the end of the EDGM feed, methanol (5 ml) and toluene (0.444 g) were added to the flask.

The conversion of EGDM and MMA was determined to be 99.7% and 99.0%, respectively (by HPLC). The molecular weight distribution obtained is a bilinear curve (by GPC), the low molecular weight portion (M _p 7,800) constituted 26 weight percent polymer and the high molecular weight portion (M _p 134,000) constituted the remaining 74 weight percent. This is compared with the 60% high molecular weight portion of Comparative 1.

Example 2

Preparation of GMA // MMA (D _p -4 / D _p -100) Copolymer with TMS-CB

The monomers and solvent used were secreted as follows. THF was prepared by distillation with sodium / benzophenone immediately before use. MMA was prepared by passing through a neutral anhydrous alumina column and subsequently distilled with calcium hydride (100 mmHg) and stored at 0 ° C. for up to 1 week. GMA was distilled (4 mmHg) and inhibited with 100 ppm t-butyl-hydroxymethyl-phenylsulfide. 1-trimethylsiloxy-1-methoxy-2-methylpropene was prepared as 2-rotary-distillation (50 mmHg).

A 250 ml round bottom three-necked flask with condenser, thermocouple, N ₂ and vacuum inlet and mechanical stirrer was dried with a heating gun under vacuum (5 mmHg) and cooled under N ₂ purge. The apparatus was placed in a 50 ° C. water bath and charged with 67.65 g of THF. After equilibrating the solvent to 50 ° C., 0.539 g of 1-trimethyl-siloxy-1-methoxy-2-methylpropene, 0.032 g of trimethylsilyl-3-chlorobenzoate and tetra (n-butyl) ammonium in THF 0.128 ml of a 0.466 molar solution of 3-chlorobenzoate was added. After stirring for 2 minutes, 1.74 g of GMA was added to the flask all at once. 1.3 ° C. exotherm was recorded. A 30 minute feed of 30.25 g of MMA was initiated 15 minutes after the GMA addition. The flask contents were held at 50.04 ° C. ± 0.4 ° C. during the MMA feed and then for 10 minutes. One hour after the end of the MMA feed, methanol (5 ml) and toluene (0.442 g) were added to the flask.

=1.982)를 나타내었으며, 저분자량 부분(M_p1.500)은 중합체의 2중량%를 구성하였고 고 분자량 부분(M_p22,000)은 나머지 99중량%를 구성한다. 벤조산으로 에폭시기를 관능화한 후(제법 2), GPC상에서 UV결과로써 이정분자량 분포(

=3.422)가 검지되었다. 저분자량 부분(M_p2,800)은 43.5%의 벤조산을 함유한 반면, 고분자량 부분(M_p19,000)은 나머지 56.5%를 함유하였다. 동일한 샘플은 원래 샘플과 유사한 분자량 분포(GPC상에서 RI 검파에 의해)를 보였다. 따라서, 단지 43.5%의 GMA 단일 중합체만이 MMA 첨가전에 종단되었으며, 비교 2에서 100%의 GMA와 비교된다.The conversion of GMA and MMA was determined to be 100% and 84.0%, respectively (by HPLC). The resulting molecular weight distribution (by GPC) is obtained by low molecular weight tail (

= 1.982), with the low molecular weight portion (M _p 1.500) making up 2% by weight of the polymer and the high molecular weight portion (M _p 22,000) making up the remaining 99% by weight. After functionalizing an epoxy group with benzoic acid (Manufacturing Method 2), bimodal molecular weight distribution was determined by UV on GPC (

= 3.422). The low molecular weight portion (M _p 2,800) contained 43.5% of benzoic acid, while the high molecular weight portion (M _p 19,000) contained the remaining 56.5%. The same sample showed a similar molecular weight distribution (by RI detection on GPC) as the original sample. Thus, only 43.5% of GMA homopolymers were terminated prior to MMA addition, compared to 100% of GMA in comparison 2.

[Method 2]

Reaction of GMA // MMA (D _p- 6 // D _p- 100) Copolymer with Benzoic Acid

GMA // MMA copolymer (prepared by Example 2) was functionalized with benzoic acid as follows.

67.4 g GMA / MMA copolymer solution (prepared in Examples 4 and 5), 9 g benzoic acid, 100 ml toluene and 100 ml propylene in 500 ml 3-neck flask with thermometer, fractionation condenser and PTFE-coated magnetic sterling bar Charged carbonate. This solution was heated to reflux with a heating mantle. About 110 ml of solvent was squeezed out until the reflux temperature reached 140 ° C. The remaining contents were refluxed at 140 ° C. for 3 hours.

At this point, 98.8% of the original epoxy content was lost (by epoxy titration).

[Comparative 2]

Preparation of GMA // MMA (D _p- 4 // D _p- 100) Copolymer

The monomers and solvents used were prepared as follows. THF was prepared by distillation with sodium / benzophenone immediately before use. MMA was prepared by passing through a neutral anhydrous alumina column and then distilled with calcium hydride (100 mmHg) and stored at 0 ° C. for up to 1 week. Glycidyl methacrylate (GMA) was distilled (4 mmHg) and inhibited with 100 ppm t-butyl-hydroxymethyl-phenylsulfide. 1-trimethylsiloxy-1-ethoxy-2-methylpropene was prepared as 2-rotary-distillation (50 mmHg).

A 250 ml round bottom three-necked flask equipped with a condenser, thermocouple, N ₂ and vacuum inlet and mechanical stationary was dried with a heating gun under vacuum (5 mmHg) and cooled under N ₂ purge. The apparatus was placed in a 50 ° C. water bath and charged with 68.02 g of THF. After allowing the solvent to equilibrate to 50 ° C., 0.534 g of 1-trimethylsiloxy-1-methoxy-2-methylpropene and 0.128 ml of 0.466 mole tetra (n-butyl) ammonium 3-chlorobenzoate solution were added. . After stirring for 2 minutes, 1.63 g of GMA was added to the flask all at once. A 1.8 ° C. exotherm was recorded. Fifteen minutes after the addition of GMA, 30.05 g of MMA was fed for 30 minutes. The flask contents were kept at 50.3 ° C. ± 0.3 ° C. during the MMA feed and for 10 minutes thereafter. One hour after the MMA feed, methanol (5 ml) and toluene (0.443 g) were added to the flask.

=4.675), 저분자량(M_p1,700)은 중합체의 6중량%를 구성하고 고분자량(M_p95,000)은 나머지 94중량%를 구성하였다.The conversion of GMA and MMA was determined to be 100% and 87.0%, respectively (by HPLC). The obtained molecular weight distribution (by GPC) was bimodal (

= 4.675), low molecular weight (M _p 1,700) constituted 6% by weight of the polymer and high molecular weight (M _p 95,000) constituted the remaining 94% by weight.

In order to distinguish the epoxy containing polymer (GMA-containing) from the block copolymer and the single-MMA polymer, the residual epoxy groups in the polymer were reacted with benzoic acid (Preparation 2). UV technology only detected benzoate esters located on GMA-containing polymers, while refractive index (RI) technology detected all polymer types present. The simultaneous use of both UV and RI techniques on the GPC output stream can determine the amount of single-GMA and block copolymer present in the polymer mixture.

=1.421)가 밝혀졌다. 이 물질의 분자량은 M_p2,700이었다. 같은 샘플은 원샘플과 유사하게 GPC상에서 RI에 의해 밝혀진 이정 분자량 분포를 나타내었다. 따라서, 모든 GMA 단일 중합체는 MMA 첨가전에 중단되었다.After functionalizing the epoxy group with benzoic acid, the molecular weight distribution was determined by UV detection on GPC.

= 1.421). The molecular weight of this material was M _p 2,700. The same sample showed a bimodal molecular weight distribution revealed by RI on GPC, similar to the original sample. Thus, all GMA homopolymers were stopped before MMA addition.

[Comparative 3]

Preparation of MMA (D _p -200) Linear Homopolymers by Multiple Monomer Feed

Chromatography with neutral anhydrous alumina prepared the MMA and stored at 0 ° C. for up to 2 weeks without inhibition. THF was prepared by distillation with sodium / benzophenone immediately before use. 1-trimethylsiloxy-1-methoxy-2-methylpropene was prepared by two-rotary strip distillation (50 mmHg).

A 250 ml round bottom three-necked flask equipped with a condenser, thermocouple, N ₂ and vacuum inlet and addition funnel, heating mantle and mechanical sterilizer was dried with a heating gun under vacuum (5 mmHg) and cooled under N ₂ purge. 104.01 g of THF was charged to the apparatus and heated to reflux (67.9 ° C.). Once refluxed, 0.8 ml of 0.1036 mole trimethylsilylacetonitrile (in THF) solution and 0.172 ml of 0.466 mole tetra (n-butyl) ammonium 3-chlorobenzoate (TBA-CB) (in THF) solution are charged to the flask. It was. 0.6750 g of 1-trimethylsiloxy-1-methoxy-2-methylpropene initiator was further charged into the flask. Immediately after loading the initiator a 20 minute supply of 19.85 g of MMA was started. The reflux temperature increased from 68.0 to 68.3 ° C. during the course of the monomer feed. After holding at the reflux temperature of the reaction mixture (68.0 ° C.) for 60 minutes, sample (A) was taken for molecular weight determination and a second MMA feed (20.20 g over 20 minutes) was started. The reflux temperature rose from 67.8 to 69.8 ° C. during the monomer feed process. The reaction mixture was again held at reflux (70.0 ° C.) for 60 minutes before taking sample (B) for molecular weight determination and starting a third MMA feed (20.15 g over 20 minutes). The reflux temperature increased from 69.6 to 71.9 ° C. during the course of this monomer feed. The reaction mixture was again held at the horney temperature (71.5 ° C.) for 60 minutes, after which sample (C) was taken for molecular weight determination and a fourth MMA feed (20.25 g over 20 minutes) was started. The reflux temperature increased to 71.6-73.9 ° C. during this monomer feed. After completion of the fourth monomer feed, the reaction mixture was held at reflux for 10 minutes, then the heating mantle was removed and the mixture was allowed to cool to room temperature for 60 minutes, then 5 ml of methanol and 0.444 g of toluene were added and sample (D) was determined for molecular weight determination. Was taken.

The molecular weight distribution of each sample was determined by GPC and summarized in Table 1 with the results of Comparative 3A using twice the silylated acetonitrile (TMS-CH ₃ CN).

Example 3

Preparation of MMA (D _p- 200) Linear Homopolymers by Multiple Monomer Feeding with Trimethylsilyl-3-chlorobenzoate (TMS-CB)

Chromatography over a neutral anhydrous alumina column prepared the MMA and stored at 0 ° C. for up to 2 weeks without inhibition. THF was prepared by distillation with sodium / benzophenone immediately before use. 1-trimethylsiloxy-1-methoxy-2-methylpropene was prepared as 2-rotary-distillation (50 mmHg).

A 250 ml round bottom three-necked flask equipped with a condenser, thermocouple, N ₂ and vacuum inlet, addition funnel, heating mantle and mechanical stirrer was dried with a heating gun under vacuum (5 mmHg) and cooled under N ₂ purge. The apparatus was charged with 105.3 g of THF and heated to reflux (67.9 ° C.). Once refluxed, 0.8 ml of 0.1036 mol (in THF) trimethylsilyl acetonitrile solution, 0.8 ml of 0.1104 mol (in THF) TMS_CB solution and 0.172 ml of 0.466 mol TBA-CB (in THF) solution were charged to the flask. To the flask was further charged 0.692 g of 1-triethylsiloxy-1-methoxy-2-methylpropene initiator. A 20 minute feed of 20.08 g of MMA was started immediately after charging with the initiator. The reflux temperature increased from 67.9 to 69 ° C. during the monomer feed process.

The reaction mixture was held at reflux (68.5 ° C.) for 60 minutes before taking sample (A) for molecular weight determination and starting a second MMA feed (20.08 g over 20 minutes). The reflux temperature rose from 67.7 to 69.5 ° C. during the monomer feed. The reaction mixture was again held at reflux (68.7 ° C.) for 60 minutes before taking sample (B) for molecular weight determination and starting a third MMA feed (20.20 g over 20 minutes). The reflux temperature increased from 67.9 to 70.5 ° C. during this monomer feed. The reaction mixture was again held at reflux (69.2 ° C.) for 60 minutes, then sample (C) for molecular weight determination was taken and a fourth MMA feed (19.75 g over 20 minutes) was started. The reflux temperature increased from 67.9 to 70.4 ° C. during this monomer feed. At the end of the fourth monomer feed, the reaction mixture was kept at reflux for 10 minutes, then the heating mantle was removed and the mixture was allowed to cool to room temperature for 60 minutes. Was collected.

The molecular weight distribution of each sample determined by GPC is summarized in Table 1 with the results of Example 3A omitting silylated acetonitrile. These results show that for all tetrapolymer feeds the polymerization is active and the molecular weight is closer to theory, resulting in the fact that less polymer chains have been lost at the first second monomer feed than in comparison 3.

TABLE 1

Molecular Weight Results of Multiple Monomer Feed Activity Test for TMS-CB Patent Example and Comparison in Reflux THF Solvent

[Comparative 4]

Preparation of MMA // EGDM (D _p- 1001 / D _p- 4) Star Polymers with TBAAC in Reflux

The monomers and solvents used were prepared as follows. THF was prepared (purified) by distillation with sodium / benzophenone immediately before use. MMA and EGDM were prepared by passing through a neutral anhydrous alumina column and MMA was subsequently distilled with calcium hydride at 100 mmHg and stored at 0 ° C. for up to 1 week. 1-trimethylsiloxy-1-methoxy-2-methylpropene was prepared by 2-rotation-distillation (50 mmHg).

A 250 ml round bottom three-necked flask with condenser, thermocouple, N ₂ and vacuum inlet and mechanical stirrer was dried with a heating gun under vacuum (5 mmHg) and cooled under N ₂ purge. The apparatus was equipped with a heating mantle and charged with 60.6 g of THF and heated to reflux (67 ° C.). At reflux, 0, .550 g of 1-trimethylsiloxy-1-methoxy-2-methylpropene and 0.575 ml of 0.1 mol (in THF) tetra (n-butyl) ammonium acetate (TBAAC) solution were added to the flask at reflux. Charged. Two minutes after the addition of TBAAC, a 30 minute feed of 30.40 g of MMA was started. The reaction was held at reflux for an additional 30 minutes during the feed and after the MMA feed. At this time, 2,70 g of EGDM was fed into the reaction flask over 10 minutes.

The contents of the reaction flask were kept at reflux for EGDM feed and an additional 5 minutes. The flask was then cooled to room temperature over 55 minutes at which time the reaction was stopped with ethanol (5 ml). Toluene (0.442 g) was then added to the flask.

The conversion and molecular weight distributions of MMA and EGDM are summarized in Table 2.

Example 4

Preparation of MMA // EGDM (D _p- 100 // D _p- 4) Star Polymers with TMS-AC and TBAAC During Reflux

The monomers and solvents used were prepared as follows. THF was prepared (purified) by distillation with sodium / benzophenone immediately before use. MMA and EGDM were prepared by passing through a neutral anhydrous alumina column and MMA was subsequently distilled with calcium hydride at 100 mmHg and stored at 0 ° C. for up to 1 week. It was prepared by 1-trimethylsiloxy-1-methoxy-2-methylpropene DMF bi-rotational distillation (50 mmHg).

A 250 ml round bottom three-necked flask with condenser, thermocouple, N ₂ and vacuum inlet and mechanical stirrer was dried with a heating gun under vacuum (5 mmHg) and cooled under N ₂ purge. The apparatus was equipped with a heating mantle and charged with 58.32 g of THF, which was heated to reflux (67 ° C). At reflux, 0.570 g of 1-trimethylsiloxy-1-methoxy-2-methylpropene, 0.575 ml of 0.1 mol (in THF) tetra (n-butyl) ammonium acetate (TBAAC) solution and 0.183 ml To this was further charged a 0.88 mole (in THF) trimethylsilyl acetate (AMSAC) solution.

A 30 minute feed of 30.92 g of MMA was started 2 minutes after TMSAC addition. The reaction was kept under reflux for an additional 30 minutes during the feed and after the MMA feed. At this time, 2.60 g of EGDM was fed into the reaction flask over 10 minutes. The contents of the reaction flask were kept under reflux for an additional 5 minutes with EGDM feed. The flask was cooled to room temperature over the next 55 minutes and at this point the reaction was stopped with methanol (5 ml). Toluene (0.442 g) was then added to the flask.

The conversion and molecular weight distribution of MMA and EGDM are summarized in Table 2 with the results for Examples 4a and 4b using various levels of TMSAC. These results indicate that polymerization is more active at the start of EGDM feed when TMSAC is added to the reaction due to better molecular weight control, higher monomer conversion and lower unattached branches (lower molecular weight) than in Comparative 4, where no IMSAC was used. Shows that This example and comparison show an improvement in molecular weight control, with conversion and unattached branches dependent on the amount of TMSAC used. All examples 4, 4a and 4b exhibit low conversion and eventually gel on standing.

[Comparative 5]

Preparation of MMA // EGDM (D _p- 100 // D _p- 4) Star Polymers as TBACB During Reflux

The monomers and solvents used were prepared as follows. THF was prepared (purified) by distillation with sodium / benzophenone immediately before use. MMA and EGDM were prepared by passing through a neutral anhydrous alumina column, and the MMA was subsequently distilled with calcium hydride at 100 mmHg and stored at 0 ° C. for up to one week. 1-trimethylsiloxy-1-methoxy-2-methylpropene was prepared as 2-rotary-distillation (50 mmHg).

A 250 ml round bottom three-necked flask with condenser, thermocouple, N ₂ and vacuum inlet and mechanical stirrer was dried with a heating gun under vacuum (5 mmHg) and cooled under N ₂ purge. The apparatus was equipped with a heating mantle and charged with 59.20 g of THF, which was heated to reflux (67 ° C). At reflux, 0.70 g of 1-trimethylsiloxy-1-methoxy-2-methylpropene and 0.150 ml of 0.38 mole (in THF) tetra (n-butyl) ammonium 3-chlorobenzoate (TBACB) were added to the flask at reflux. The solution was charged further.

Two minutes after the addition of TBACB a 30 minute supply of 30.49 g of MMA was started. The reaction was kept under reflux for an additional 30 minutes during the feed and after the MMA feed. At this time, 2.60 g of EGDM was fed into the reaction flask over 10 minutes. The contents of the reaction flask were kept at reflux during EGDM feed and for an additional 5 minutes. The flask was cooled to room temperature over the next 55 minutes, at which point the reaction was stopped with methanol (5 ml). Toluene (0.446 g) was then added to the flask.

Conversion and molecular weight distribution of MMA and EGDM are summarized in Table 2

Example 5

Preparation of MMA // EGDM (D _p- 100 // D _p- 4) Star Polymers with TBACB and TMSAC During Reflux

The monomers and solvents used were prepared as follows. THF was prepared (purified) by distillation with sodium / benzophenone immediately before use. MMA and EGDM were prepared by passing through a neutral anhydrous alumina column, and the MMA was then distilled with calcium hydride at 100 mmHg and stored at 0 ° C. for up to 1 week. 1-trimethylsiloxy-1-methoxy-2-methylpropene was prepared by 2-rotation-distillation (50 mmHg).

A 250 ml round bottom three-necked flask with condenser, thermocouple, N ₂ and vacuum inlet and mechanical stirrer was dried with a heating gun under vacuum (5 mmHg) and cooled under N ₂ purge. The apparatus was equipped with a heating mantle, charged with 58.20 g of THF, which was heated to reflux (67 ° C). At reflux, 0.580 g of 1-trimethylsiloxy-1-methoxy-2-methylpropene, 0.150 ml of 0.38 mole (in THF) tetra (n-butyl) ammonium 3-chlorobenzoate (TBACB) was added to the flask at reflux. The solution and 0.325 ml of 0.88 mol (in THF) trimethylsilyl acetate (TMSAC) solution were further charged. Two minutes after the addition of TBACB, a 30 minute feed of 30.26 g of MMA was started. The reaction was held under reflux for an additional 30 minutes during the feed and after the MMA feed.

At this time, 2.55 g of EGDM was fed into the reaction flask over 10 minutes. The contents of the reaction flask were kept under reflux for an additional 5 minutes with EGDM feed. The flask was cooled to room temperature over the next 55 minutes at which time the reaction was stopped with methanol (5 ml). Toluene (0.445 g) was added to the flask at this time.

The conversion and molecular weight distributions of MMA and EGDM are summarized in Table 2. Comparing this result with Comparative 5, in these situations, the addition of a silylated oxyanion catalyst prepared from a stronger GTP oxyanion catalyst (higher pKa in DMSO) than that used for polymerization improves the activity of GTP polymerization. It did not appear to. The results show that the polymerization is less active at the start of the EGDM feed because of the higher molecular weight unattached branches than in comparison 5 where IMSAC was not used at all. Nevertheless, monomer conversion is comparable.

Example 6

Preparation of MMA // EGDM (D _p- 100 // D _p- 4) Star Polymers with IMSCB and TBAAC During Reflux

The monomers and solvents used were prepared as follows. THF was prepared (purified) by distillation with sodium / benzophenone immediately before use. MMA and EGDM were prepared by passing through a neutral anhydrous alumina column, and the MMA was subsequently distilled with calcium hydride at 100 mmHg and stored at 0 ° C. for up to 1 week. 1-trimethylsiloxy-1-methoxy-2-methylpropene was prepared as 2-rotary-distillation (50 mmHg).

A 250 ml round bottom three-necked flask with condenser, thermocouple, N ₂ and vacuum inlet and mechanical stirrer was dried with a heating gun under vacuum (5 mmHg) and cooled under N ₂ purge. The heating mantle was installed in this apparatus, 59.42 g of THF was charged, and it heated to the reflux temperature (67 degreeC). At reflux, 1.3 ml with 0.530 g of 1-trimethylsiloxy-1-methoxy-2-methylpropene and 0.575 ml of 0.1 mol (in THF) tetra (n-butyl) ammonium acetate (TBAAC) solution in a flask To this was further charged a 0.11 mole (in THF) trieticsilyl 3-chlorobenzoate (TMSCB) solution. Two minutes after the addition of TBACB, a 30 minute feed of 30.43 g of MMA was started. The reaction was maintained at reflux for an additional 30 minutes during the feed and after the MMA feed. At this time, 2.60 g of EGDM was fed into the reaction flask over 10 minutes. The contents of the reaction flask were maintained at EGDM feed and reflux for an additional 5 minutes. The flask was cooled to room temperature over the next 55 minutes, at which time the reaction was stopped with ethanol (5 ml). Toluene (0.445 g) was added to the flask at this time.

The conversion and molecular weight distributions of MMA and EGDM are summarized in Table 2.

Comparing these results with comparison 4, the addition of silylated oxyanions (lower pKa in DMSO) than the oxyanion catalysts used for the polymerization increased the activity of the GTP polymerization. The reason is that the obtained molecular weight is closer to the theoretical value and there are fewer unattached branches.

TABLE 2

Claims (6)

Under polymerization conditions, at least one polar acrylic-type alpha olefin monomer is (i) quaternary organosilicon, organotin, having at least one activating substituent or activating diradical attached and having one or more substituents which are inert under polymerization conditions or Organic germanium polymerization initiator, and (ii) contact acid with a catalyst which is an oxyanion having a pKa (DMSO) of 5-24 or a salt consisting of an oxyanion and a cation, and (iii) no activating substituents or activating diradicals At least one equivalent of R ₃ Si-group per mole of oxyanion compound (R contains one or more ether oxygen atoms in its aliphatic component and one or more functionalities which are non-reactive under polymerization conditions) P of a conjugated acid, not a polymerization initiator, containing hydrocarbyl of up to 20 carbon atoms containing a sex substituent) A process for preparing an "active" polymer, characterized in that it is also contacted with a polymerization activity enhancer selected from the group consisting of 0-silylated esters or ether modifications of oxyanion compounds with a Ka (DMSO) of 5-24. The process according to claim 1, wherein the enhancer (iii) contains the same R ₃ Si-group as the polymerization initiator (i). The process according to claim 1 or 2, wherein the enhancer (iii) concentration is in the range of 0.1-200 moles per mole of catalyst. The process of claim 1 wherein the enhancer (iii) concentration is in the range of 2-25 moles per mole of catalyst. 2. The process of claim 1 wherein catalyst (ii) is a source of 3-chlorobenzoate and enhancer (iii) is trimethylsilyl ester of 3-chlorobenzoate. The process of claim 1, wherein the conjugate acid of the activity enhancer (iii) has a lower pKa (DMSO) than the pKa (DMSO) of the conjugate acid of the catalyst (ii).